2, 4-bis(methylsulfonyl)-benzeneazo-nu-hydroxyalkyl-nu-beta-cyanoethylaniline compounds



Patented Aug. 18, 1953 UNITED STATES ATENT OFFICE 2,4 BIS (METHYLSULFONYL) -B ENZENEAZO- N HYDROXYALKYL-N fi-OYANOETHYL ANILINE Coll/[POUNDS I Joseph B. Dickey and George J. Taylor, Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application June 30, 1951, Serial No. 234,682

6 Claims. (Cl. 260-2075) I i Y OzCHa X wherein R. represents a fi-hydroxyethyl group, a -hydroxypropyl group, a firy-dihydroxypropyl group, a fi-sulfatoethyl group, a 'y-sulfatopropyl group or a sulfated Bn-dihydroxypropyl group, X represents a hydrogen atom, a chlorine atom, a bromine atom or a methyl group and Y represents a hydrogen atom, a methoxy group, an ethoxy group or a B-hydroxyethoxy. group are valuable dyes for coloring textile materials made of or containing a cellulose alkyl carboxylic acid ester having 2 to 4 carbon atoms in the acid groups thereof. They are particularly of use for the coloration of cellulose acetate textile materials. They color the aforesaid textile materials orange to rubine shades which have good to excellent fastness to light and gas. Those compounds containing a sulfato group also have utility for the dyeing of silk, wool, polyethylene terephthalate and modified polyacrylonitrile textile materials. Because of the increased water solubility of the new sulfato azo dye compounds, they are particularly adapted for dyeing cones of yarn and fabrics of close weave and of heavy construction.

It is an object of our invention to provide new azo compounds. Another object is to provide a satisfactory process for the preparation of the new azo compounds of the invention. A further object is to provide dyed cellulose alkyl carboxylic acid ester textile materials which possess excellent fastness to light and gas. A particular object is to provide new azo compounds which are especially of value for the dyeing of cellulose acetate textile materials.

By cellulose alkyl carboxylic acid esters having two to four carbon atoms in the acid groups thereof, we means to include, for example, both hydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate-propionate and cellulose acetatebutyrate.

The new azo compounds of our invention are prepared by diazotizing 2,4-bis(methylsulfonyl)- aniline and coupling the diazonium compound obtained with a compound having the formula:

| oHaCHzCN R, X and Y in the foregoing formula have the meaning previously assigned to them. The new sulfato azo compounds are also prepared by introducing a sulfato group into the azo compounds of our invention not containing a sulfato group.

The following examples illustrate the azo compounds of our invention and their manner of preparation.

EXAMPLE 1 A. Nitrosyl sulfuric acid 7.6 grams of dry sodium nitrite were added, with stirring, to 92 grams of sulfuric acid (sp. gr. 1.84) while keeping the temperature below C. The resulting solution was then cooled to 5 C.-10 C. and grams of acetic acid were added dropwise, with stirring, while maintaining the temperature at 5 C.10 C.

B. Diazotz'zation 24.9 grams of 2,4-bis(methylsulfonyl) -aniline were added slowly, with stirring, to the nitrosyl sulfuric acid prepared as described above while keeping the temperature below 20 C. Then, 100 grams of acetic acid were added dropwise, with stirring, at a temperature between 15 C.-20 C. and stirring was continued until all the 2,4-bis- (methylsulfonyD-aniline had dissolved and diazotization was complete. The diazonium solution thus formed was then poured onto 500 grams of crushed ice and enough urea was added to destroy the excess nitrous acid. The diazonium solution should be clear and free of suspended undiazotized amine.

O. Coupling 19 grams of N-p-hydroxyethyl-N-p-cyanoethylaniline were dissolved in 200 cc. of ice and Water containing 15 cc. of hydrochloric acid (sp. gr. 1.16) and the diazonium solution prepared as described in B was then added slowly, with stirring. The coupling reaction which takes place was completed by adding just sufiicient sodium carbonate to neutralize the acid present in the reaction mixture. The sodium carbonate was added portionwise. The dye compound formed was recovered by filtration, washed well with water and dried. It has the formula:

omomcu v EXAIWPLE 8 ride and the resulting solution was cooled to and colors cellulose acetatfi textile -'.-;nateria1s;

orange shades.

EXAMPLE 2 24.9 grams of 2,4-bis(methylsulgqnylianilinel were diazotized and the W w I obtained was coupled with 22.4 grams of'N ,8 droxyethyl N B cyanoethyl-m-chloroaniline.

Diazotization, coupling and recoueny'cf-tthedye compound formed were carried out in accordance with the procedure described in Example 1.. The dye compound obtained colors cellulose acetate textile materials soarlet shades.

1 02C. fl hen 12.7 grams of freshly distilled ..24.9 .e rams..0.f-. z e simethylsulfony :aniline werefldiazotized. and: he; idiazoniu n compound obtained was coupled with 25.4 grams of,.N,-,-,3- hydroxyethyl N [3 cyanoethyl 2 methoxy- 5-chloroaniline. Diazotizatien, coupling and recovery of glya-.-c ornpound-jgrnred were carriedout in accordance with the procedure described in Example 1-. Theidye-cornpound ,obtamed-colors cellulose: acetate textile-materials rubine shades.

-24.9-- grams -of 2;4-bismethylsulfonylManiline were diazotized and the diazonium compound obtained was coupled;,with .;20.4 grams of N-vhydroxypropyl N [i cyanoethylaniline. Di- .azofriza iona'caun in nan .ecoueryaofz-th ady omneundimrm riedeout 11;..accordnce; withrtilenraeednr-.sies z :ibed., ncExamulezlhe dye.c 1 pmind:cli aineddmlorsacellulose.acee ate. extileematerial r n e-shades.

ifE A LE' 6 4-9: emms J-M tm ul qny-Dmanilin were diazotized and thediazonium Ecegugn und obtainedwas;.coupled.-.-with- Edd ami e. N dhydroxre hyl N e5 1 0yan .e rlem1bta ai 1111 uantization..couplineand reco r. Hhe dye. compcunddormcd werena ied ou ;in. .-ac.-. corda nce with the procedure deseribedgn gggarnpie 1. The dye compound obtained colors cellulose acetate textiles-materials.scarlet shades.

anagrams f di-bi meth sulignylk nil ne wer d a ci zedz and th idiaz nium..q mnmmd a n was co l d ith-20 4, r ms. f. N-fird reih l iN"-" l3 cyanqethyle rtql din etion.,.c1 inean mewwrnfihe .d e. eeme f m dw reparried.outinaqqo idan e W' h"t e'n 9 re de c ibed 'fixarnpl he d e wmpol d, b in col .ca luki e acetate textilematerlals'red'shades.

stirringovena'period of 3 hours. After the addition of'the chlorosulfonic acid, the reaction mixtureqwasLslowlywarrned to 50 C. and maintained at this temperature for several hours. Heating wasthen discontinued and the carbon tetrachloride was distilled off under reduced pressure.

3 9 0 con otice and water were then added to the reaction mixture and the dye was recovered by SOzCHa It colors the aforementioned textile ma terials orange shades.

CHQCHgOS OaNa EXAM LE. 9

45:5 grams of 2,4-bis(methylsulfonyl) -benzeneazo N 'y -hydroxypropyl N- B- cyanoethylaniline (i. e. the dye compound of Eiample 5) were dissolved in 20?) cc. of pyridine and t he resultingsolution was cooled to 5 G. Then 12.7 grams of chlorcsul'fonic acid were added dropwise, with stirring, over a period of 3 hours. Stirring was continued-for an additional-2 hours following which the reaction mixture was heated to 50 Qandmaintained at this tempe ratureyfor twohours. Following this reaction mixture was c ooled' and the pyridine removed" under" reduced pressure. 3QQ cc; of ice and water were then added to; the reaction 'rnixture and the dye was recoyered -by evaporation. The dyecompound"obtainedfcolorsthe aforesaid textile materials orange shades.

. 48.5 grams of 2,4-bis(methylsulfonyl-) -benzeneazo N ,8 hydroxyethyl" N p cyanoethyl m-chloroaniline (i. e. the dye compound of Examplefl) were mixed with 50 cc o'f 'sulfur-ic acid-(sp. gr: 1.84) and-thereakztion mixtu're iesuitingwaswarmedto--50 C; for'3 hours and then cooled foo-02C; 200 cc. of-ice 'and 'water were added .and thenthe reaction mixture -'w' asinade neutral'to Congored paper by the'gradual addition-of sodium'bicarbonate. The dye compound formedwas recovered by filtration and; 'i yashed with a cold aqueous sodium chloride solution. Thedye compoundfithus obtained colors t he aforesaid-nxaterials scarlet shades.

2.4 3 grams 9% 4 m hylfiu ian .-.a l n were diazotized and the di'azoniu'm compound obtained was coupled.wi th 35.7 gram'sf' fithe piing and recovery of the dye compound formed was carried out in accordance with the procedure described in Example 1 except that the dye was washed with an aqueous sodium chloride solution rather than water. The dye compound obtained colors the textile materials mentioned hereinbeiore rubine shades.

From the foregoing examples the manner of introducing a sulfato group is believed to be clear, especially since the manner of introducing a sulfato group is known to those skilled in the art. Any other suitable way of introducing the sulfato group into the dye molecule can be employed. The sulfato group can be present in its free acid form or in the form of an inorganic or organic base salt such as, for example, the Na, K, N54, Mg, Ca, Li, methylamine, dimethylainine, trimethylamine, pyridine, aniline, guanidine, semicarbazide, biguanidine, phenyl guanidine, cyclohexylamine, dicyclohexylamine, tetrahydrofurfurylalnine or alkanolamine salt form.

Other coupling compounds that are used in the preparation of the azo compounds of our invention include, for example, N-fixy-dihydroxypropyl-N-B-cyanoethyl-m-chloroaniline, N-BgydihydroXypropyl-N-B-cyanoethyl-m-toluidine, N- 5, -dihydroxypropyl-N-e-cyanoethyl-2-methoxy- 5-chloroaniline, N c hydroxyethyl-N-e-cyanoethyl-243-hydroxyethoxy-5-chl0roaniline, N-fmdihydroxypropyl-N-fi-cyanoethyl 2-,8-hydroxyethoxy-5-chloroaniline, N-[i-hydroxyethyl N-ficyanoethyl-2-methoxy-5-bromoaniline, N-[i-sulfatoethyl-N-p-cyanoethyl-m-bromoaniline, N-ysulfatopropyl-N-fl-cyanoethyl m chloroaniline, N-y-sulfatopropyl-N-e-cyanoethy1-2-methoxy-5- chloroaniline, sulfated N-fl y-dihYdlOXYPlODYl-N- ,e-cyanoethylaniline, sulfated N ,B,' dihydroxypropyl-N-B-cyanoethyl-m-chloroaniline and sulfated N-fi -dihydroxypropyl-N-fl-cyanoethyl-2- methoxy-5-chloroaniline.

The new azo compounds of our invention may be advantageously directly applied to the material undergoing coloration in the form of an aqueous suspension which can be prepared by grinding the dye to a paste in the presence of a sulfonated oil, soap, sodium lignin sulfonate, or other suitable dispersing agent and dispersing the resulting paste in water. While an aqueous suspension has been referred to it will be understood that some of the dye goes into solution, and this is particularly so in the case of the sulfato dye compounds. Thus, the dye bath will contain dye in solution as well as in suspension.

Direct dyeing operations can, with advantage, be conducted at temperatures of about 70 C'.90 C. but any suitable temperature can be used. Thus, the textile material such as cellulose acetate, for example, to be dyed or colored is ordinarily added to the dye bath at a temperature lower than that at which the main portion of the dyeing is to be effected. A temperature approximating 45 C.-55 C., for example, following which the temperature is raised to that selected for carrying out the dyeing operation. The temperature at which the dyeing is conducted may, of course, be varied somewhat depending upon the particular material undergoing coloration. As is understood by those skilled in the dyeing art, the intensity of dyeing can be varied by varying the proportion of dye to material undergoing coloration. The amount of dye 5 used can be, for example, /3 to 3% (by weight) of that of the textile material, although lesser or greater amounts of dye can be used.

We claim:

1. The azo compounds having the general formula:

I l OzCHs X wherein R represents a member selected from the group consisting of a ,B-hydroxyethyl group,

CHzCHzCN a 'y-hydroxypropyl group, a ,B,' -dihydroxypropyl group, a ,c-sulfatoethyl group, a -sulfatopropyl group and a sulfated B; -dihydroxypropyl group, X represents a member selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom and a methyl roup and Y represents a member selected from the group consisting a hydrogen atom, a methoxy group, an ethoxy group and a B-hydroxyethoxy group.

2. The azo compound having the formula:

OHzCHzOH 3. The azo compound having the formula:

CHzCHzCN n CH2CH2OH o5 CHaO2S- N-=N N\ A OHzCHzCN 4. The azo compound having the formula: /CH1CHOHCHOH C H3 O 23- N=NON\ CHzOHnCN O2OH3 5. The azo compound having the formula:

JOSEPH B. DICKEY. GEORGE J. TAYLOR.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,082,156 Felix et a1 June 1, 1937 2,147,338 Felix et a1. Feb. 14, 1939 2,156,446 Bock May 2, 1939 2,492,971 Dickey Jan. 3, 1950 

1. THE AZO COMPOUND HAVING THE FORMULA: 